CN107810252A

CN107810252A - Boudouard reaction for the hydrolysis of the combination water that manufactures methane

Info

Publication number: CN107810252A
Application number: CN201680031286.7A
Authority: CN
Inventors: 卡尔·维尔纳·迪特里希
Original assignee: Individual
Current assignee: Individual
Priority date: 2015-06-24
Filing date: 2016-05-21
Publication date: 2018-03-16
Also published as: DE112016002823A5; WO2016206669A1

Abstract

Carbon dioxide from combustion of natural gas or release and the carbon of coal are converted into carbon monoxide (reaching Bu Duaer balances in carbon monoxide side) at a temperature of higher than 800 DEG C.Carbon monoxide by the hydrogen obtained by the electrolysis water of electric energy with being converted into methane.Methane is imported into natural gas transmission network and stores and transports in natural gas transmission network.Natural gas burns in a manner of without CO2 emission.Store carbon dioxide as the raw material of the electric energy for methane manufacture and transport in natural gas transmission network.The second-time burning in terms of calculating of the carbon of coal.

Description

Boudouard reaction for the hydrolysis of the combination water that manufactures methane

The present invention relates to a kind of method for second-time burning carbon, and wherein carbon and vapor is by adding carbon dioxide conversion For forming gas or carbon monoxide, and forming gas or carbon monoxide are converted into methane with additional hydrogen, are led to using electric energy Cross electrolysis and obtain the hydrogen, and methane is imported into natural gas transmission network, and extract and fire from gas transmission network The equivalent of methane or the methane in natural gas is burnt or discharged, and separates and collect carbon dioxide from burning gases, its The carbon dioxide of middle collection is used in forming gas or carbon monoxide manufacture.

During natural energy utilization, it is maximum the problem of be that superfluous wind energy and the sun are generated because of natural conditions Energy.Reach common understanding in the industry at present, corresponding solution can not be found only by electric power means.It is unnecessary as outlet Electric energy can be used for electrolysis water to manufacture hydrogen.

Hydrogen can be introduced into natural gas, and mixes common conveying with natural gas.But so meet again Another problem is arrived：The difference of the basic physical features and combustion characteristics of hydrogen and natural gas is obvious.From volume, natural gas Density be the octuple of hydrogen, calorific value is three times of hydrogen, and oxygen demand in combustion is four times of hydrogen.

The wind energy and solar energy of fluctuation can also produce the hydrogen stream of fluctuation under electrolysis, and when hydrogen stream is drawn After entering natural gas, the mixed airflow of fluctuation will be produced.The mixed gas of such hydrogen and natural gas, its storage, Transport and application method, in the patent announced《DE 10 2010 020 762 A1》(the transport of regenerative resource and steady It is fixed) and patent《DE 10 2010 031 777 A1》(storage of the hydrogen in natural gas vessel).In addition, in the patent In, for how to stablize regenerative resource, also illustrate a general method.Mixing of these methods for the Wave type Gas is introduced to the market and a kind of obstacle.

Also another method conveying hydrogen, i.e., synthesize methane by chemical method by hydrogen and carbon dioxide.First Alkane is almost the main component of natural gas, therefore can be stored in no obstacle in gas pipeline.There are numerous items all It is relevant with this problem.Carbon dioxide mentioned here, can be isolated from the burning waste gas in thermal power plant to, or It is isolated from biogas.The technique that carbon dioxide is separated from biogas is not described later in detail to raw material；Carbon dioxide From the separation in burning waste gas up to storage technology (CCS), due to lacking the accreditation of masses, therefore prospect how, be not also not Know number.

In terms of economy point, in order to superfluous regenerative resource, traditional carbon geochemistry be selected to react, i.e. coal (carbon and water channel moral mol ratio are 1 for charcoal and water:Reaction between 1, according to chemical equation 1), at elevated pressures and temperatures, Produce carbon monoxide and hydrogen.The mixed gas that hydrogen and carbon monoxide are formed with identical mol ratio, hereinafter simply referred to as " synthesis Gas ".Then electrolysis water is carried out according to chemical equation 3 by wind energy and solar energy again, so as to manufacture hydrogen, and according to two Mol ratio again, by electrolysis water, caused hydrogen flow guide enters in " forming gas ".Then according to chemist " Sa Shane Battier " The chemical reaction of name, manufactures methane and water, and both mol ratios are 1:1 (referring to chemical equation 2).

Chemical equation 1.) C+H₂O=CO+H₂

Chemical equation 2.) (CO+H₂)+2H₂=CH₄+H₂O

Chemical equation 3.) 2H₂O=2H₂+O₂

Method as described above, go out not influence the methane of weather by the wind energy and solar energy production of coal and surplus. Such methane belongs to mixed type methane, and its carbon used comes from fossil fuel, and protium then come from wind energy and Solar energy.In chemical balance, power supply network release electric energy, and methane is produced by adding coal, such methane possesses day The feature (hereinafter referred to as " mixing methane ") of right gas, and it is introduced into gas pipeline.Coal is then the carrier of storage energy.

According to the forming gas containing mixing methane caused by the chemical equation 1 to 3, it is transported to energy storage power generation and sets After applying, it will be permeated and burnt and (carry out combustion reaction according to chemical equation 4).After forming gas and natural gas mixing By combustion reaction (according to chemical equation 5), important synergistic effect can be produced.

Chemical equation 4.) CO+H₂+O₂=CO₂+H₂O

Chemical equation 5.) CH₄+2O₂=CO₂+2H₂O

Chemical equation 1 to 5 described above will be repeatedly referred to further below, this five chemical equations are abbreviated respectively For Rk.l to Rk.5.

In addition to coal, other compounds (prioritizing selection comes from plant) containing carbon also can be used to produce institute State forming gas.Plant material mentioned here, such as trees, the composition of its maximum level is exactly carbohydrate, and carbon Carbon and water in hydrate can produce hydrogen and carbon monoxide after reaction.

, must while the forming gas containing carbon monoxide is produced by electrolysis water because carbon monoxide is containing toxic It must be produced in strict accordance with quantity as defined in chemical equation 2 (according to the symmetrical principle of dosage).For the safety of protection staff, i.e., Make to produce according to chemical equation 1 and 2, it is also necessary to avoid producing or build up an excess amount of carbon monoxide.

The main contents of the invention, it is using carbon and comes from the dump energy of supply network, manufactures first Alkane, and hydrogen is manufactured by electrolysis water, then methane is mixed with hydrogen, the final gaseous mixture for producing hydrogen and carbon monoxide Body.This kind of mixed gas is exactly to be mixed by converting coal or carbon compound with vapor, and according to chemical balance and symmetry Dosage directly generate forming gas, main component methane therein will be imported into natural-gas transfer pipeline.

The content of the preferred embodiment of the present invention especially describes in the claims.

Another preferred embodiment is characterised by, the methane being so incensed that by carbon monoxide or forming gas with electrolysis hydrogen To be flowed back on 60% to 85% efficiency of the electric energy used in electrolysis.

In order to avoid carbon monoxide is imported into gas transmission pipeline, it should be noted that all carbon monoxide must be thorough The carbon monoxide decomposited in mixed type methane, or mixed type methane is converted into, before gas pipeline is imported into, it is necessary to quilt Fully burning.It is recommended that before mixed type methane is imported into gas pipeline, to containing for the carbon monoxide that does not react away thoroughly wherein Amount is detected.

Carbon monoxide is thoroughly converted into mixed type methane, can also reduce the waste to hydrogen.Superfluous hydrogen can To be stored in mixed type methane.According to current standard, the methane of natural gas transmission pipe is imported into, hydrogen content therein is most It is big to allow ratio 5% (plan license from now on to 10%).

Therefore, the invention also includes a content, that is, is introduced into the mixed type methane of gas pipeline, can contain most High 10% hydrogen.

According to the technique of this invention design, superfluous wind energy or solar energy, can obtain larger journey in supply network The absorption of degree, and after coal is added, methane can be converted into, and import into supply network.The premise of this invention It is not require nothing more than equipment there is higher capacity, and requires to be connected with power supply and gas pipeline.For equipment, have been contemplated that Necessary capacity is arrived.In addition, in circuit system, equipment should be connected with high voltage network, and in air-channel system, equipment must It must be connected with hyperbar network (remotely supplying network).In order to meet this requirement, in addition to the conveyance conduit of correlation, also need Want additional investment transformer and gas compressor.

But in mutually the technique of design is invented according to this, if equipment is connected with gas electricity generator, then described extra Investment can save.In fuel gas generation facility, equipment may be coupled on high-voltage transmission network, can also and natural gas Gas transmission network is connected.Electric energy in vortex can be introduced into high-voltage transmission network after high pressure is converted to.In addition, electric energy Low pressure can also be reduced to from high voltage network, so that cell reaction needs." energy storage power generation facility is first by coal (carbon) for this item patent Element is converted to methane ", comprising following all equipment, in items of equipment, then there occurs the chemical reaction 1-5 marked in bracket.

1. power generating equipment/fuel gas generation facility (optional chemical equation 4 and/or 5)

2. coal distillation apparatus, and the production equipment of forming gas.(chemical equation 1)

3. electrolysis installation, for converting electrical energy into hydrogen (chemical equation 3)

4. hydrogenation equipment, for hydrogenating carbon monoxide, it is set to be converted into hydrogenated methane (chemical equation 2)

5. the interface of grid, and it is furnished with transformer.

6. the interface of natural gas transmission network.

When using the equipment, in the operation phase that is different, being alternately present, energy utilization aspect two can be run into most Big challenge：The energy of surplus how is made full use of, and in the case where power supply electric energy is unstable, how to allow supply network Electric current keeps stable.

In a kind of operation phase (in the patent be referred to as first stage), using fuel gas generation facility (1), so as to when wind energy and When the natural causes such as solar energy cause power supply breach, this breach can be made up, or supply network can be allowed stable.Mixed type The methane either natural gas or forming gas equivalent with its calorific value, is sent or overflows from gas transmission network (6), electric energy leads to Transformer is crossed to be input into supply network (5).Part 2 to 4 in equipment, is not at running status.

Another operation phase (in the patent as second stage), (superfluous) electric energy is discharged in supply network 5, and And hydrogen is converted into 3.According to this invention, from the forming gas of the raw material such as coal production in 2, with hydrogen 4 In common reaction produce hydrogenated methane.Electric current is released from supply network (5), and hydrogenated methane is introduced into natural gas line (6) in.Equipment 1 (power generating equipment) is now not at running status.

By this stage, mixed type methane can be by the fuel value of electric energy the combination coal of surplus, with natural gas or together Deng the form of combustion value gas, it is stored in gas pipeline, is discharged into power generating equipment when needed.Storage can thus be defined The maximum feature in energy type power plant, exactly gets up still untapped energy stores, is discharged again when needing.Entirely Equipment is exactly a kind of compound energy storage power generation facility, and mixed type methane is stored in gas pipeline, what compound methane was stored In whole energy, only half comes from stored dump energy (second half energy comes from coal).Gas pipeline conduct Energy storage device, its advantage are exactly to have huge memory capacity.

In the invention, a kind of compound energy storage power generation facility is referred to, foregoing set is contained in such power generating equipment Standby 1 to 6, in equipment 5 and 6 wherein, the meeting of gas and electric energy is flowed towards both direction, and size can alternately change, And gas pipeline then serves energy accumulator effect.

According to different demands and different operation phase, the equipment 1 to 4 can be turned on and off.But in order to The conversion of energy and material is carried out in such devices, on condition that equipment must possess higher flexibility.These flexibility bodies In present fuel gas generation facility (1) and electrolysis wetting system (3).The hydrogenation process (4) of carbon monoxide (gas phase therein, can input Nitrogen catalyst) it can then perform or delete according to the actual requirements.

The flexibility and the destructive distillation of coal of this invention requirement and the manufacturing process (2) of carbon monoxide are unrelated.Although institute Stating the power of equipment can be adjusted, but the hydrogenation process (4) of the electrolytic process for synchronously carrying out (3) and carbon monoxide, Then can not arbitrarily it be turned on and off.In addition, warned as discussed above, to the important transitional product of carbon monoxide, it is necessary to keep away Exempt from its accumulation.

Equipment 2,3,4 is connected into after power generating equipment (1) according to this invention, had an advantage that：Made in equipment 2 The forming gas produced, its calorific value is very close to coal gas used in everyday in city, and the process run in power generating equipment In, individually it can be released jointly (referring to chemical equation 5) (referring to chemical equation 4) or with natural gas.Therefore, It is responsible for the equipment 2 of manufacture forming gas, under described two running statuses, can runs, so in fuel gas generation facility (4) It is middle to manufacture electric energy and when manufacturing mixed type methane (chemical equation 2), use equipment 2 with can switching.

In the first operation phase, have in a kind of operational mode, in order that supply network is stable, allow fuel gas generation therein The destructive distillation device and synthesis gas production equipment (2) of facility (1) and coal are operated together, while discharge forming gas.In addition, Natural gas can also be extracted from gas pipeline.If necessary, natural gas can also mix with forming gas, and jointly Release, while electric energy is imported into supply network.In this mode, equipment 3 and 4 is not run.

Another content of this invention is can to select forming gas, on the one hand as fuel gas, can with it is natural Gas is used in mixed way, or the power generation energy resource for the fuel gas generation facility being used for as independent fuel in the first operation phase, another Aspect, with being used in conjunction with using electric energy by electrolysis water and caused hydrogen, in the second operation phase, for producing mixed type Methane.Therefore, in two operation phase, the destructive distillation of coal is able to continue progress.

According to this invention, the regenerative resource by using coal and surplus in fuel gas generation facility is mixed to produce Gas is closed, is also had another " synthesis energy efficiency ", you can to widen the water supply source in electrolysis water.In forming gas can Combustion gas body hydrogen or methane and (chemical equation 4 or 5) after oxygen reaction, can form condensed water.Be free of and appoint in this condensed water What salt, meet the necessary condition of electrolysis water.One mol of hydrogen can produce one mole of water.And if to be obtained by electrolysis water 2 moles of hydrogen, according to chemical equation 3, then 2 moles of pure water is needed, and according to chemical equation 2, pass through combustion of methane Salt-free condensed water can be obtained, this 2 moles of pure water is just provided.According to pure calculating, in whole technological process Salt-free water can be obtained, during electrolysis and this by being required for when wind energy and solar energy production methane according to this invention Water.After combustion of natural gas, 2 moles of condensed water (referring to chemical equation 5) can be obtained, this 2 moles water just turns into Required water in chemical equation 3.

During electrolysis water, 1 megawatt of electric energy is often consumed, 200 to 250 cubic metres of hydrogen can be produced and (depended on In different energy utilization efficiencies), and need the salt-free pure water (distilled water) of about 160 to 200 liters of consumption.It is assumed that The fuel gas generation facility that one production capacity is 100MW/h, the equipment of equipment is also 100MW/h to the absorptive capacity of dump energy, that The distilled water needed for electrolysis water is 16000 to 20000 liters to the power generating equipment per hour.It means that purchase distilled water is used In electrolysis, it is necessary to costly expense, therefore cost and the energy will turn into a big problem.

The condensed water that power generating equipment obtains is a kind of appropriate output, can be as former material cheap in electrolysis hydraulic art Material.From natural components, this condensed water not saliferous, carbonic acid, sulfuric acid and hydrosulphuric acid containing faint concentration, but acidity Very low (pH value is about 4.5).Carbonic acid can discharge from water, and mineral acid can be by anion exchange, with condensed moisture From.

Further, it is also possible to condensed water is obtained by identical principle from gas warming installation (" burning type warmer "). For warming installation of the power more than 60 kilowatts, in order to which in accordance with public morality principle, all condensed waters it must be being ensured It can be discharged into chemistry in neutrality in irrigation canals and ditches.Therefore, if condensed water is built up together, for involved by this invention And technique in be then a kind of cost-effective scheme.

If forming gas is in gas power station and natural gas mixes burning, and the condensed water after burning according to Identical mode is used for electrolysis water, then needs in advance to do forming gas special processing.Coal can be as the life of forming gas Raw material is produced, but can also contain up to 4% sulphur compound in coal, and sulphur compound must be fully burned.Coal Sulfide can be combined in caused gas after charcoal burning, this point is known.Further, coal can produce in retort process Raw iron oxide.Therefore, the cleaning process of forming gas is critically important, can quilt because the caused mixed type methane from forming gas Import into gas pipeline, and can also have natural gas in gas pipeline, requirement of the gas pipeline to clean-up performance is very high. Based on this point, if outwards release, and only using again after forming gas is separated with natural gas in fuel gas generation facility Caused condensed water (2 moles of water) is used to be electrolysed after net gas burning, and effect then more preferably (can please contrast chemical equation 3 With 5).

In invention described above, its content is additionally included in fuel gas generation facility (1), caused by after combustion of natural gas The collection and utilization of condensed water, the raw material using condensed water as cell reaction (3).Obtained according to chemical equation 2,4 and 5 Condensed water, cell reaction (chemical equation 3) and hydrogenation (chemical equation 2) institute after this are just provided Need.

The technique designed according to this invention is used the composite part in the equipment 2,3,4, that is, utilizes wind Energy or solar energy, from coal or other carbon compounds, manufacture mixed type methane.The feature of mixed type methane, and ring The natural gas of guarantor's type is equally matched.After the technique merges with energy utilization technology, the natural gas in gas pipeline can be progressively Ground is eliminated by composite gas, is also no longer needed for relying on the natural gas of import.

It is caused after coal destructive distillation and electrolysis water and hydrogenation of carbon monoxide reaction are added in fuel gas generation facility " synthesis energy efficiency " is summarized as follows respectively：

If coal retort process (process that forming gas is manufactured according to chemical equation 1) is one uninterrupted During technological process, then advantage can be embodied in production technology.It means that in the second operation phase (with reference to chemical reaction Formula 2) during manufacture mixed type methane, and in the first operation phase in fuel gas generation facility (with reference to chemical equation 4) When discharging gas, then need to use forming gas.

(with reference to chemical equation 3) during electrolysis water, in order to carry out hydrogenation according to chemical equation 2, it is Hydrogen necessary to ensure, in addition to containing hydrogen in forming gas, it is also necessary to 2 moles of water.Wherein one mole of water, Can be out of the second operation phase (i.e. chemical equation 2), directly by separating condensed water acquisition and storing；Another mole Water, it can condense and obtain from the flue dust of fuel gas generation facility, then store in the first operation phase.In other words, it is used for The hydrogen of manufacture mixed type methane comes from the condensed water in two operation phase in production equipment.In the process, equipment 1, 2nd, 3 and 4 be interconnected, therefore chemically accurately calculate, for pure water necessary to manufacturing mixed type methane, can obtain To accumulation and storage.

If switch on natural gas line, and also connect high-voltage transmission network, then within the different operation phase, Gas and electric current can convey towards different directions, and all devices can use.That is natural gas line and its interface and height Pressure power transmission network and interface can be used in conjunction with by all devices.Power plant is equipped with the extensive transformer of range, so as to Within the first operation phase, electric current is changed from vortex, and then inputted in high voltage network.And in the second operation phase, Same transformer, then the electric energy in high voltage network can be converted to relatively low voltage, so as to meet the needs of cell reaction. For mixed type energy storage power generation factory, the part in its electric power storage energy comes from the electric energy of surplus, and a part comes from from coal The mixed type methane produced.This kind of mixed type methane will be delivered into gas pipeline, need to use when can be from appendix Discharged again in road.Therefore, gas pipeline serves the effect of accumulator in mixed type energy storage power generation factory.It is also another Accumulator, it is exactly cistern.

For the mixed type energy storage power generation factory designed according to this invention, in order to focus on its economy, 1,000,000 thousand are often stored Watt dump energy and about 80 tons of coals are added again, can about produce the mixed type methane of 13 ten thousand steres, it is assumed that combustion The energy utilization efficiency in gas power plant is 65%, and uses condensed water, then 850,000 kilowatts can be provided in demand peaks Electric energy, and gas can discharge again, and in the case of without using coal, energy utilization efficiency can reach 85%.

The regenerative resource of nature can cause excessive or very few energy input into supply network, therefore will cause Two operation phase are alternately changed.In order to make the electric current of supply network stable, can use high heating value, have wide range of applications Coal.Coal had better not be but used, but uses the natural gas (mixed type methane) harmless to weather.

In order to consider the ecological balance, the dosage of hydrogen can be increased step by step, hydrogen still passes through electrolysis water (chemical reaction Formula 3) obtain.Together with hydrogen and the mixed type methane blended for being imported into natural gas line.According to newest standard, hydrogen exists Addition in natural gas, 10% can be reached.

According to chemical equation 3, in oxygen caused by electrolysis water, it can be collected and store, be used to synthesize afterwards The burning of gas (chemical equation 4) or natural gas/methane (chemical equation 5).After the nitrogen in eliminating air, Can avoids producing nitrogen oxides in combustion.Nitrogen oxides is to the extent of damage of weather considerably beyond carbon dioxide. After electrolysis water, oxygen sinks because density is larger, therefore purity is higher than combustible gas, easily liquefies and with liquid Form stores.

During using pure oxygen burning, the ignition temperature of fuel gas is higher, and energy density is larger, and this is advantageous to The utilization ratio of energy is improved, but the temperature of various materials is also close to the respective high temperature resistance limit.Here recommend addition cold But water, and condensed water is preferentially used as cooling water, to monitor ignition temperature.The condensed water and evaporation energy consumed, It can be reclaimed again by condensed water after being combusted.And the carbon monoxide contained in combustible gas can also be recovered, and And the carbon dioxide isolated from flue dust can also recycle.

If forming gas is burned in the first operation phase, then is evaluated in terms of CO2 emission, this portion Division technique belongs to increase carbon emission.Consider from ecological balance angle, coal can be converted to not by using the energy of surplus The methane of climatic environment is damaged, for using later.So only have one it is trickle the shortcomings that, be exactly within the first operation phase, Excessive natural gas can be produced in gas power plant with mixing methane.In addition, empirically, it is flammable for generally The conveying of the solids such as the delivery ratio coal of gas is more effective.

On the other hand, according in the technique of this invention design, when according to chemical equation 2 to coal destructive distillation, use The natural raw material such as some timber (or partly using), it is more helpful to the ecological balance.Timber as carbohydrate, according to Chemical equation 1 can be converted to forming gas.Charcoal and hydrogen can synthesize " biological methane ".In order to improve the ecological balance, Hydrogen can be added in the methane for importing gas pipeline, because hydrogen can be with completely burned, and any pernicious gas will not be discharged.

After the mixed type methane to weather non-hazardous being obtained from the regenerative resource of surplus and coal, real economy Profit is apparent.Individual states only need coal, therefore the import to natural gas eliminates the reliance on.Using coal and superfluous electric energy as The energy storage power generation factory of basic energy resource, is increasingly turned to the utilization of regenerative resource, so as to realize the technological process of most economical saving.

The industrialization designed according to this invention, its economic benefit is substantially estimated as follows：By the mistake residual electricity of 1 gigawatt Energy, the mixed type methane of 13.5 ten thousand steres can be about produced, these mixed type methane or suitable with its calorific value Natural gas discharges again, for producing, can obtain about 850,000 kilowatts of energy and (refer to " electricity in this paper conclusions Chemical simulation calculates ").

Carbon in these mixed type methane, 60 to 80 tons of coal is taken around, in other words, use about 70 tons Coal, and the dump energy of 1 gigawatt, 850,000 kilowatts of high value energy can be produced, can demand peaks afterwards When come into operation.

The power plant of other non-flexible types, such as thermal power plant or nuclear plant, when the generated energy of power generating equipment Beyond the maximum load-carrying capacity of power transmission network, superfluous electric energy can be also produced.It is that big power station imitates to economy to have individual present situation Benefit is seen heavier, and current stage expansion is relatively good using the time of regenerative resource, because regenerative resource is being powered There is preferential right in network.Either it is envisioned that the electric energy deficiency in supply network at present, or be exactly surplus.

In the power plant of such non-flexible type, mixed type energy storage power generation facility can be built according to this invention.First, Mixed type methane can be manufactured with the electric energy of surplus, and methane is imported in gas pipeline, after this, works as gas power plant When being peaked to the demand of energy, these combustible gases can be discharged.(master) power generating equipment therefore can preferably energy efficiency Continuous running.Forming gas can be inputted in the combustion chamber of main power generating equipment if necessary, with methane co-fire.

In existing power plant, the output voltage of generator generally is 5000 volts.The input of common electrolysis installation Voltage is generally between 200 to 300 volts, and in electrolysis unit, after all electrolysis cells are sequentially connected in series connection, each connect Voltage is only 2.2 volts.The sum of the unit of these series connection, it has to be restricted, because even one of electrolysis cells are sent out Raw failure, whole electrolysis installation can be all closed, it is necessary to which integral device is repaired.If all electrolysis cells are divided into some Individual module, there is the series connection electrolysis unit of identical quantity in each module, and also additionally retain a spare module, then can be with Increase the sum of many electrolysis cells.Even if there is a failure in these operating all modules, then extra to retain That spare module can open, impaired module can be closed, and be waited to be repaired.Therefore, electrolysis unit can imports Of a relatively high voltage, safe operation.The input voltage can and power generator of electrolysis unit match, and high pressure is defeated Transformer in power network, in two operation phase, two kinds of equipment are all suitable for.Voltage difference between generator and electrolysis installation (and voltage difference between main transformer), can be balanced by transformer.

If mixed type energy storage power generation facility is located near lignite power plant, then just more for excellent on geographical position Gesture because there can directly take lignite, when energy storage power generation factory to the demand of the energy it is contemplated that during ground increase, lignite can be with One car transports power plant to connecing a car.Direct combusting brown coal, this still controversial movement, is modified, lignite conduct in the future It the economical energy, should more reasonably be used, prior function should be played in energy enterprise.The use of coal must The decree of current ecology aspect must be observed.

Chemical equation general view (chemical equation 1-5)

Rk.1.)C+H₂O=CO+H₂

Rk.2.)(CO+H₂)+2H₂=CH₄+H₂O

Rk.3.)2H₂O=2H₂+O₂

Rk.4.)CO+H₂+O₂=CO₂+H₂O

Rk.5.)CH₄+2O₂=CO₂+2H₂O

Rk.6.)CO₂+4H₂=CH₄+2H₂O

(1-5 marked in bracket is the chemical equation that every equipment is related to each equipment general view of mixed type energy storage power generation factory Numbering)

1. power generating equipment/fuel gas generation facility (chemical equation 4 and/or chemical equation 5)

2. coal distillation apparatus and synthesis gas production equipment (chemical equation 1)

3. electrolysis installation and rectifier, for adjusting the electric energy (chemical equation 3) of manufacture hydrogen

4. for the equipment (chemical equation 5 and 6) for being hydrated carbon monoxide (or carbon dioxide), manufacturing mixed type methane

5. the interface of high-voltage transmission network and transformer (chemical equation 4,5 or 3)

6. the interface (chemical equation 5 or 2) of natural gas pipeline

On energy storage device or energy storage medium

Most important energy storage device, it is exactly combustible gas conveyance conduit in fact, mixed type methane therein is just deposited as energy Store up medium.When requiring the expenditure of energy, stored mixed type methane or can be with the combustible gas of its equal fuel value It is released in combustible gas conveyance conduit, is mixed with the natural gas of there, this release process is preferably carried out in gas power plant, Therefore energy storage power generation facility should be had in such power plant.After various kinds of equipment is integrated, how to act synergistically has in detail above Thin description.In addition, discharging again for energy storage gas can also be carried out in an independent place, then natural gas then should be from natural gas Discharge in pipeline, mixed with the combustible gas of methane or equal fuel value.

Carbon dioxide industry can also be separated and stored from flue dust.In combustion, if with electrolysis water produce Oxygen substitutes air, then after condensation of water, these carbon dioxide just seem unnecessary.If these carbon dioxide are allowed also to enter Enter gas pipeline to be conveyed, then in coal burning, coal inevitably produces carbon monoxide with carbon dioxide reaction. These carbon monoxide can be refluxed into combustion chamber, to avoid flowing into air.

The medium of another storage energy is exactly the water for electrolysis, and these water are generally from one or more combustion gas hairs Condensed water in the flue dust of electric facility.If fuel gas generation facility is connected with compound energy storage power generation facility, then just Condensed water can be collected on the spot at the scene, it is standby to be electrolysed according to corresponding capacity storage in cistern.If fuel gas generation Facility does not connect with compound energy storage power generation facility, then the condensed water being collected, mixing can only be transported to by water storage car Type energy storage power generation facility.In course of conveying, the condensed water in heating installation can also be collected simultaneously.How from natural gas and mixed Collected in the combustion process of mould assembly combustion gas and store condensed water, and therefore can isolate mixed type first again from mixed gas Alkane (referring to chemical equation 2,3 and 5), and one of content of this invention.That is collected out during combustion of natural gas is cold Condensate has higher purity, and therefore, according to this invention, the condensed water for electrolysis will be extracted preferentially from by coal Forming gas combustion process in the condensed water collected.

Manufacture and use on forming gas

In the first order of " fischer-tropsch process flow " (Fischer-Tropsch), carbon and vapor by pressing at high temperature Reacted according to chemical equation 1 and produce forming gas.Depending on coal or the different quality of carbon compound, the reaction Caused main matter is carbon monoxide and hydrogen afterwards, may also have some methane.Can also coal is empty in isolation Under conditions of gas, 1000 to 1300 degrees Celsius are heated to, obtains coke.This is favorably improved the purity of carbon, and is advantageous to Be converted to forming gas.1 ton of coal can produce about 300 cubic metres of coal gas, and wherein main component is about 50% hydrogen With 30% methane, these gases can directly be imported into gas pipeline, can also continue to react according to chemical equation 2.Coal After destructive distillation, other byproducts can be produced, such as " coal tar " is the mixture of various aromatic substances in fact.Coal tar is always It is considered as the basic material of chemical industry.The technique designed according to this invention, Coal Energy Source can be rationally utilized, improve ecology Environment, and substantial amounts of intermediate chemicals is obtained, and also the dependence to petrochemical industry can be reduced gradually.

In the technique of described two production forming gas, it is included in the cleaning process of gas, and set in energy storage power generation In two operation phase applied, it is impossible to continuously and uninterruptedly switch.Therefore, this invention has a special contribution, is exactly two In the individual operation phase, under different service conditions, forming gas can be used (according to chemical anti-in the first operation phase Answer formula 3 to use forming gas, forming gas is used according to chemical equation 4 in the second operation phase).

If coal power generating equipment (thermal power generation facility) is also built on the side of mixed type energy storage power generation facility, then In the second operation phase, forming gas can also be blown into the combustion chamber of thermal power generation facility and discharge there.When When reaching peak value to the demand of energy, other fuel gas can be additionally added, relatively high power can be rapidly achieved.Therefore, coal Charcoal power generating equipment has larger independent and flexible.

Forming gas is converted to compound methane according to chemical equation 2, and its process belongs to according to chemist's Sa Shane Battier (Sabatier) one of chemical reaction of name.In such reaction, in the presence of nitrogen catalyst or iron catalyst, an oxygen Change carbon to be hydrogenated by hydrogen, produce methane.Such chemical reaction belongs to exothermic reaction, the other techniques designed according to this invention In, if necessary to absorb heat, the heat of this reaction release can be utilized, therefore energy utilization efficiency when forming gas discharges can be with Further lifted.

In the reaction carried out according to chemical equation 3, if be suitably modified, additionally it is possible to macromolecular hydrocarbon is obtained, Can be as the fuel of automobile.

The release and storage of forming gas/carbon dioxide

Discharge forming gas, it is meant that its calorific value of direct or indirect utilization, to obtain electric energy.

In carbon dioxide caused by the stage that forming gas is released, it can also be stored or be sieved.For example, hydrogen After caused water is condensed after burning, carbon dioxide can be isolated from flue dust by high-pressure liquefaction.Caused by electrolysis water Oxygen, is used for combustion-supporting if instead of air, therefore need not be blown into air, then after vapor is condensed, titanium dioxide Carbon turns into unique gas, is directly stored.

During forming gas is discharged, for forming gas in addition to directly burning, carbon monoxide therein can be with Reacted with vapor, produce carbon dioxide and hydrogen.Resulting carbon dioxide will be stored, after this, only Hydrogen is burned.Just as by electrolysis water obtain hydrogen, carbon dioxide can be allowed to be changed to methane, that is, allow hydrogen and storage Carbon dioxide is reacted according to chemical equation 6, can also allow hydrogen with forming gas or carbon monoxide according to chemical anti- Formula 2 is answered to be reacted.Forming gas can also be divided into two parts, and a portion is used for manufacturing hydrogen and carbon dioxide, separately A part of forming gas reacts for manufacturing methane with hydrogen according to chemical equation 2.In the release process of forming gas In, methane can be also produced, these methane both directly can burn or discharge, and can also store.

For conclusion, forming gas can be released or burn as pure hydrogen or pure methane.In three species altogether In the forming gas of type, carbon dioxide therein can be separated, and be stored.

Suggest herein：Preferably when compound energy storage power generation facility need not consume electric energy and will not produce discharge Wait, forming gas is converted into methane.

In technique according to this invention design, if forming gas comes from the bion energy (such as trees), then In the stage of release forming gas, carbon dioxide can be stored in underground (because carbon dioxide is easily absorbed by plants). While storing dump energy, bion methane is produced.

In the mixed gas of carbon dioxide and methane, the proof on its bion source

The atmospheric carbon dioxide and methane formed as final product is according to its source (biology or fossil) or is output Or economically convey (such as biological methane).It is important, therefore, that ought the part of conversion of such as timber and coal gasified When, it is determined that the biological ratio in above-mentioned gas.

It can be determined by " carbon isotope radioactive method " existing in radiology (C14 methods)：Used bion Raw material and the bion methane thus manufactured, risen by isotope assay in terms of C14 Isotopic moieties with identical Initial value.And C14 isotopes are not included in fossil class carbon.For the source of carbon dioxide, methods described is equally applicable.Can With according to being referred to as the radiocounting tube method of " Luo Bifa (Lobby) " then " gas is measured.

Electrochemical Simulation when using coal and (superfluous) electrical energy production mixed type methane calculates

Start to produce according to chemical equation 3 (electrolysis water).It is assumed that energy efficiency during electrolysis is 80%, then is often produced One cubic metre of hydrogen needs 4.2 kilowatts of electric energy.According to chemical equation 2,2 moles of hydrogen is also needed in forming gas, For manufacturing mixed type methane with reaction of carbon monoxide.Therefore, 1 cubic metre of mixed type first is often produced from forming gas Alkane, about 8.4 kilowatts of electric energy is needed altogether.

Here it is assumed that the carbon in mixed type methane, all is from coal.Carbon mass ratio in methane is 75% (molecular weight of methane is 16,12) atomic weight of carbon therein is.The gaseous density of methane is 718 grams/cubic metre. Therefore, learnt by calculating, 1 cubic metre of methane, wherein containing 539 grams of carbon.Usually used raw coal, wherein carbon member Plain degree content is 65% to 90% (quality for depending on raw coal).So every cubic metre of mixing methane needs 580 to 830 grams Raw coal.

In summary, 8.4 kilowatts of (superfluous) electric energy and 580 grams to 830 grams (dehydration) raw coal, Ke Yisheng are passed through The mixed type methane of 1 cubic metre of production.The fuel value of mixed type methane is similar to natural gas.Every cubic metre of mixed type methane is released After putting, can provide 7.5 kilowatts electric energy (interior energy of every cubic metre of mixed type methane be 11.5 kilowatts, the energy of gas power plant If the usage amount that amount service efficiency is assumed to 65%. raw coal is 580 grams of mark in bracket, after mixed type methane release Energy ecology be 87%.

The stabilisation of the release of forming gas/hydrogenation of carbon monoxide reaction

The stage is discharged in gas, forming gas is converted into heat energy by the burning in power generating equipment.Forming gas Release can be carried out in coal power generating equipment or fuel gas generation facility.According to the demand to energy, set in fuel gas generation In applying, while forming gas is discharged, natural gas can also be discharged simultaneously.

Gas discharges the stage, and the storing process of energy temporarily ceases.Deposited according to the energy in the technique of this invention design Storage process belongs to a chemical process as coal retort process, wherein needing the participation of carbon monoxide.It is if now right The demand of power is relatively low, then the process of hydrogenation of carbon monoxide and then generation methane is preferably also disposed at this stage.

Even if being participated in without hydrogen caused by electrolysis water, gas release process can be also carried out.In the process, forming gas In hydrogen can be separated.Then according to 2,2 moles of hydrogen being separated of chemical equation, and other 1 mole of hydrogen with And 1 mole of carbon monoxide combination is converted to methane in forming gas.The stage is discharged in gas, the manufacturing process of methane is relatively low It can be carried out under power.Remaining carbon monoxide or the forming gas containing carbon monoxide, then should set according to this invention The technique of meter is discharged into power generating equipment.

In the hydrogenation process of carbon monoxide, if thoroughly carbon monoxide remains in methane unreacted, then this kind of Reactant mixture temporarily should be burnt in power generating equipment.Need to avoid carbon monoxide from being blended into gas pipeline herein In (as safe precaution measure, the carbon monoxide content in ultimate product methane can be checked).Because the hydrogenation of carbon monoxide The release stage of process and forming gas is carried out simultaneously, if so producing extra combustible gas, then be favourable on the contrary Phenomenon.Power generating equipment is united with hydrogenation of carbon monoxide facility, and a kind of new synthesis technique.

The backflow of Electrochemical Simulation calculating/gas

How according to chemical law, the correlation between the quality of reactant and product, energy, volume is calculated, will It is described in detail below.Calculate when, agreement forming gas be hydrogen and carbon dioxide mixture, but carbon dioxide and The mixed proportion of hydrogen can flexibly change, depend primarily on raw material property (such as bion raw material or coal etc. change Stone-type raw material) and its pyrogenic distillation gasification method.In addition, in forming gas, it is allowed to penetrate into the methane formed in advance.

Memory phase：Energy/mass/volume

The reference capacity energy of electric energy can be stored：1 gigawatt

If to manufacture 1 cubic metre of hydrogen by electrolysis water, 0.8 liter of pure water and 4.2KW energy are taken around (utilization rate 80%.)

According to chemical equation 2 and 3,2 parts of hydrogen (containing forming gas) and 1 part of methane will be produced.

It means that 1 cubic metre of methane is, it is necessary to 8.4 kilowatts/1 gigawatt, and need 600-800 grams of coal Charcoal.

Therefore, the methane of 12 ten thousand steres is manufactured, then needs about 85 tons of coal.

Storage facility

The condensed water only isolated from flue dust, just need to be stored and (stored in the second operation phase).This just anticipates Taste,

When combustion of natural gas, the pure water of 0.8x 2x 120000=192000 liters can be produced, i.e.,

192 cubic metres of pure water

When forming gas burns, the pure water of 0,8x 1x 120000=96000 liters can be produced, i.e.,

96 cubic metres of pure water

The second holder being equipped with for gas pipeline, prepares for all predictable situations, to ensure to have foot Enough capacity.

The backflow of gas

In fuel gas generation facility, the methane of 12 ten thousand steres, when capacity usage ratio is 65%, about 850,000 can be produced Kilowatt energy.

(it is assumed that the energy of 1 gigawatt produced without using raw coal, capacity usage ratio are) 85%

Conclusion

- coal and superfluous energy can be used for manufacturing methane, and these methane can be stored in gas pipeline, and are transported It is defeated, then it is released with 85% utilization rate (ratio of air-flow and electric current).

- under different operation conditions, electric energy will alternately be absorbed by mixed type energy storage power generation factory and store or be arranged Put.

- mixed type methane is suitable with the quality of the natural gas of H- grades.

- 1 cubic metre of mixed type methane is, it is necessary to which about 700 grams of coals and 8 kilowatts of dump energy produce.

- the energy stored, utilization rate when it is played back (it is also required to provide about 60 to 80,000 during every megawatt of electric energy playback Gram coal) be about that 85% (numerical value floats between 75% to 90%, depending on energy of the power generating equipment in gas backstreaming Measure utilization rate)

- by adding coal, the electrolytic speed of water can improve more than 2 times.

- using bion raw material when, all bion carbon raw materials used, its can stored electric energy will be turned Turning to bion methane, (in bion gas facility, carbon not only generates methane, also 30% to 50% titanium dioxide Carbon).

It stored carbon dioxide, can be reacted with hydrogen, generate methane.Compared with forming gas, with dioxy , it is necessary to use 2 times of hydrogen when changing carbon manufacture methane.

Three chemical equations below, describe the mechanism that methane is regenerated from flue dust：

A.) the burning CH of methane₄+2O₂>CO₂+2H₂O

B.) the electrolysis 4H of water₂O>4H₂+2O₂

C.) the regeneration CO of methane₂+4H₂>CH₄+2H₂O

Chemically reaction equation C) in it can be seen that, with carbon dioxide regenerate methane during, it is necessary to put into 4 moles Hydrogen, but manufacturing methane with forming gas only needs 2 moles of hydrogen.Correspondingly, in above-described production technology, it is imitated Rate (capacity usage ratio) is referred to as " efficiency that electric energy is converted to combustion gas ".Integral energy utilization rate is about between 35 to 40% (electric current is converted to air-flow).

Chemical equation A/B/C describes the feature of the energy storage power generation facility of chemical industry type.In a wherein operation phase, Methane is released and burnt, and so as to produce energy (chemical equation A), then carbon dioxide is separated from flue dust, is obtained Storage.In another operation phase, stored dump energy is used to electrolysis water, so as to generate hydrogen (chemical equation B), then these hydrogen carry out hydrogenation to stored carbon dioxide, produce methane (chemical equation C).Chemical anti- The water generated in formula A and C is answered, is separated by condensing, is then used to cell reaction (chemical equation B).(change in electrolysis water Learn reaction equation B) during, in addition to hydrogen, oxygen is also created, oxygen can be used for the burning of methane (to change after being stored Learn reaction equation A), therefore air need not be blown into again.Therefore, flue dust is made up of carbon dioxide and vapor, and vapor is condensed And after separating, gaseous carbon dioxide can be stored directly.Certainly, carbon dioxide and vapor can also be used as gaseous mixture Body, it is stored together.

Advantageously, very unresponsive storage is proportionally added in the manufacture according to the present invention of forming gas Carbon dioxide, so as to which the carbon dioxide to be converted to the carbon monoxide of reactivity.

Because forming gas is in high temperature (at 800 DEG C to 1000 DEG C) generation, carbon dioxide to be inserted or with having produced Hydrogen reaction produce carbon monoxide and water or the reaction of the carbon with still suffering from produces carbon monoxide.Under any circumstance, Change from carbon dioxide to carbon monoxide causes the consuming of the hydrogen in forming gas.

According to the amount of the carbon dioxide of addition, the forming gas that hydrogen is consumed is obtained.In extreme circumstances, in carbon Carbon monoxide is only obtained when being in equal proportions with the mole of carbon dioxide.

Can be that carbon dioxide-forming gas adds reactant mixture methane or natural gas to improve hydrogen ratio.

The hydrogen consumed by the conversion by means of carbon dioxide, must be by adding in being produced according to the methane of the present invention Electrolysis hydrogen substitution.In these cases, when only also carbon monoxide be present, methane is unlike in synthesis gas caused by every mole 2 moles of electrolysis hydrogen is needed in the case of body like that, but needs 3 moles of electrolysis hydrogen.Generally speaking also it is applicable the 17th The chemical equation B of page, 4 mol of hydrogen are needed to form methane per mole of carbon dioxide according to the chemical equation.It is described The power of conversion is the balance (chemical equation D) between carbon monoxide and carbon dioxide, one in the case of higher than 800 DEG C Carbonoxide side reaches complete equipilibrium.

D.)C02+C<>2CO

Will it is confirmed that：According to Sa Shane Battier principle carbon monoxide and hydrogen significant reaction than unresponsive carbon dioxide Faster.

Preferably (ratio is made by carbon and reaction of the water at 800 DEG C to 1000 DEG C according to fischer-tropsch process flow in forming gas Chemical equation 1 compared with page 2).Here, in terms of what is considered is stoichiometry, because the water root remained in forming gas According to so-called " water gas shift reaction ", in cooling down forming gas, reaction produces hydrogen and carbon dioxide.Therefore, less than 500 DEG C At a temperature of, the balance shown in chemical equation D is appeared in carbon dioxide side.Carbon dioxide reacts in Sa Shane Battier Under conditions of without reaction or it is more significantly slower than the carbon monoxide in forming gas react so that only endless site preparation is carried out The formation of methane.

Therefore, in order in carbon dioxide by means of the conversion according to the present invention of forming gas or carbon in not anti- Carbon dioxide is regenerated at the end of answering again in cooling, it is necessary to when manufacturing forming gas when starting with mol ratio 1:1 removes It is equal to the water of the addition of carbon dioxide.

Therefore, in carbon with mol ratio 1:1 by means of only obtaining carbon monoxide in the conversion of carbon dioxide, and borrowing in carbon Help obtain forming gas in the conversion of vapor as carbon monoxide and the mixture of the equimolar amounts of hydrogen.

It is for what intermediate range was applicable：Carbon dioxide and water must be always complementary to one another so that amount to 1 mole of dioxy Change carbon He Shui and one mole of carbon reacts.

It should be noted that 3 moles of carbon monoxide and 2 moles of forming gas in the manufacture according to the present invention of methane Need to be electrolysed hydrogen to form methane.Therefore, the efficiency in the first scenario substantially 60% in backflow, and at second In the case of such as the efficiency substantially 85% described in chapters and sections " Electrochemical Simulation calculating ".

It is two characteristic points for chemical aspect：

Forming gas manufactures：C+H2O=CO+H2

Therefrom form methane：(CO+H2)+2H2*=CH4+H20

Boudouard reaction：C+C02=2CO

Therefrom form methane CO+3H2*=CH4+H20

(H2 provided with * is electrolysis hydrogen)

Therefore, a content of the invention is the method for second-time burning carbon, wherein carbon and vapor with titanium dioxide The form of carbon mixing is converted into forming gas or carbon monoxide, and forming gas or carbon monoxide are converted into additional hydrogen Methane, the hydrogen is obtained by electrolysis using electric energy, and methane is imported into natural gas transmission network, and from gas transmission Extraction and burning or the equivalent of discharge methane or the methane in natural gas in network, and separate and receive from burning gases Collecting carbon dioxide, it is characterised in that the carbon dioxide of collection is used in forming gas or carbon monoxide manufacture, and This supplements 1 mole of carbon dioxide and vapor on 1 mole of carbon, and the molar fraction of water and carbon dioxide is from 1:0 reaches To 0:1.

What methods described had high flexibility and allowed the supply to electric energy and the change for carbon dioxide can Mastery is reacted, and its reclaimed water/carbon dioxide is than change.

Will it is confirmed that：The subsequent second-time burning of the methane as caused by carbon dioxide.

It is also predefined, forming gas is formed when higher than 800 DEG C, forming gas and additional hydrogen forms methane Carry out according to the chemical reaction of Sa Shane Battier principle but in the case of less than 300 DEG C.Therefore it may first have to terminate carbon and water The conversion of steam and carbon dioxide and carbon, then forming gas or carbon monoxide are according to Sa Shane Battier principle and other hydrogen Solid/liquid/gas reactions produce methane.

Therefore, present disclosure (going back) is related to by hydrogen and forming gas manufacture methane, the hydrogen utilization storage Electric energy obtains producing by the way that carbon and carbon compound are gasified under conditions of carbon dioxide is added and the forming gas by electrolysis It is raw, it is characterised in that separate and store the carbon dioxide of addition from the flue dust of combustion of natural gas, and will carbon dioxide with The water that hydrogen in forming gas is formed in addition to carbon monoxide when changing considers the manufacture for forming gas in this way, with As for the water for not having residual not react in final product.

Particularly advantageously, coal first in the case where completely cutting off air coking (compare page 12, chapters and sections " forming gas/ Manufacture and application ") and then by obtained coke and carbon dioxide with mol ratio 1:1 according to chemical equation D preferably 800 DEG C to being converted into carbon monoxide in fluid bed at a temperature of 1000 DEG C.In addition, from the gas mixing obtained in coking Hydrogen Separation, the admixture of gas are mainly made up of hydrogen, methane and carbon monoxide in thing, and hydrogen is aoxidized with one Carbon is combined to form forming gas, and the forming gas is used subsequently to form methane with electrolysis hydrogen.

The residual gas obtained after hydrogen is separated can burn, and provide for being made up of coke and carbon dioxide The process heat of carbon monoxide.Because residual gas includes the harmful substance being contained mostly within coal, can be by institute Harmful substance is stated from burning gases according to method separation common in coal burning and removing.

Here, advantageously, it would be heated to 1000 DEG C of coke and directly continue reaction generation carbon monoxide with carbon dioxide.

It is also advantageous that forming gas is manufactured in original place during methane is formed and will separated with coke-stove gas Hydrogen produces methane with the electrolysis hydrogen solid/liquid/gas reactions correctly measured in terms of stoichiometry.

Carbon dioxide to be re-formed can be led to from the flue dust, mixed type methane or natural gas of conbustion synthesis gas Cross cooling or high-pressure liquefaction separation.

Suitable carbon dioxide is obtained when natural gas/methane being decomposed into hydrogen and carbon dioxide in converter.It is this Converter, which is located at, to be used at the hydrogen deposit station of the motor vehicle with fuel cell, and natural gas is changed into the fuel cell Hydrogen and in this as accessory substance produce carbon dioxide.

The present invention allows, and the wind energy or solar energy of fluctuation are stored and transported in gas transmission network in combination with cheap coal And electric energy is reconverted into high efficiency.Pass through the dioxy that will be separated at the release of mixed type methane or natural gas (backflow) Change carbon to lead back to and process the carbon dioxide in forming gas manufacture, the method according to the invention can also realize fossil The release without carbon dioxide of class energy carrier such as coal or natural gas.

Methods described causes the decarbonization of the economy of energy to accelerate, wherein the carbon in repeated combustion coal.

When producing carbon monoxide or forming gas by carbon, water and carbon dioxide, stoichiometry aspect and balance are drawn Following correlations：When higher than 1000 DEG C, reach in the conversion of carbon and carbon dioxide in carbon monoxide side 100% it is flat Weighing apparatus.

Under the same conditions, forming gas is produced by carbon and vapor.

It is difficult to produce pure methane by unpurified coal.However, import the methane in natural gas transmission network Must be pure, because the purity requirement to natural gas is high.In order to according to for manufacture methane according to the present invention Method obtains pure composition, preferably takes following manner：

First by carbonization of coal, that is to say, that heated in the case where completely cutting off air at substantially 1000 DEG C.

Here, produce the relatively pure carbon in coke form.

In addition, so-called coke-stove gas, a kind of mixture being made up of hydrogen, methane and carbon monoxide are formed.

For example via molecule sieve separation hydrogen from coke-stove gas, the hydrogen insert forming gas or carbon monoxide and The hydrogen reduces the demand to additional electrolysis hydrogen.

It is in itself high-purity in the Nature to be electrolysed hydrogen.

Last composition, carbon dioxide has been pure, because pure combustion of natural gas produces pure titanium dioxide Carbon.

The admixture of gas remained after by Hydrogen Separation also includes the harmful substance of a variety of coals.Advantageously, in order to Process heat is provided, had in carbon with being burnt in the endothermic reaction of carbon dioxide or water and being isolated from burning gases Evil material.

In order to improve the hydrogen ratio in forming gas, also natural gas can be inserted in forming gas manufacture.

, also can be in converter by methane point in the case of by means of separating carbon dioxide release methane or natural gas Solve as hydrogen and carbon dioxide, and both gases are separated.Then hydrogen is discharged and according to the present invention by carbon dioxide It is converted into methane.The advantages of methods described form, is, compared with from flue dust, carbon dioxide is more simply separated herein, And hydrogen can result in produces electric energy in fuel cell, this is preferable especially in electronic traffic.

Carbon dioxide also can be collected, stored and be transported in the original place of its formation to re-forming according to the present invention. On the contrary, then also the energy stored in methane made according to the present invention is transported to the first in natural gas transmission network The position of alkane backflow.

Present disclosure further relates to following equipment, and the equipment includes：

- be used to reach the device that Bu Duaer is balanced in carbon monoxide side, in said device from methane or natural gas Release or burning in the carbon dioxide that separates reacted with carbon.

- be used to make carbon monoxide or carbon dioxide form the device of methane by the hydrogen from electrolysis.

Methods described is also suitable for, and runs heater with natural gas under conditions of release carbon dioxide is avoided, preferably Condensing heating system.

Here, in condensing heating system, after it will react water condensation and separation, by the flue dust mixture pressure of residual It is retracted and CO 2 high pressure liquefies and as liquid from the nitrogen separation for keeping gas phase, wherein the flue dust mixes owner To be made up of carbon dioxide with the nitrogen from combustion air.

Here, it is advantageously able to by admixture of gas compressing heating, being made up of carbon dioxide and nitrogen to pass through It is preferred that the circulation loop cooling of low-temperature heating system.So obtain the condensing heating with (unidirectional) heat pump for being connected to downstream System.Carbon dioxide has been the reliable refrigerant for motor vehicle air conditioner.

Carbon dioxide is contained in trap and taken out via valve.Subtracting when then nitrogen is discharged and depressurized can be passed through Pressure is cooled down to cool down the trap (mol ratio CO2 and N2 substantially 1:8).

Therefore, present disclosure further relate to natural gas run heating indoor system, the heating indoor system by Condensing heater, heat pump and carbon dioxide trap are formed, and wherein flue dust is compressed simultaneously after by aqueous condensate separation And the flue dust mixture by compressing heating sends its heat to heat cycles loop in heat exchanger, and from cooled Nitrogen separation in admixture of gas by the carbon dioxide of high-pressure liquefaction in cold-trap with holding gas phase.

Natural gas without CO2 emission is burnt while also having according to the firing equipment of the present invention The heat of effect is as condensing heating system.Due to utilizing heat pump simultaneously, so-called low-temperature heat is preferable.

The carbon dioxide isolated is stored in high-pressure bottle to liquid immediately.However, it is also possible to as cooled So-called dry ice in container realizes storage.

Scattered carbon dioxide obtaining and storage can be collected and transport to energy storage power generation facility, according to the present invention At the energy storage power generation facility, by means of hydrogenating the carbon dioxide by being electrolysed obtained hydrogen by (unnecessary) electric energy Form methane and methane is directed back in gas transmission network.Therefore, do not discharge carbon dioxide when with heated by natural gas and fire The natural gas of burning is directed back in gas transmission network as methane.

By means of the firing equipment according to the present invention and the method performed with the firing equipment, fossil class can be used natural Gas by carbon dioxide is arranged only be zero in a manner of heat.It is included in the heating indoor system of natural gas in energy interim plan, and And this by heat pump by carbon dioxide separation even also there is favourable thermomechanical effect.

The effect that can not be replicated by means of the power generating equipment with carbon dioxide separation.Here, two for example in flue dust Carbonoxide separation includes the washing with significant energy loss.Also can be with the cheap carbon dioxide that enough amounts provide Preferable reserve substance, for two level energy carrier hydrogen is converted into similar methane.

For example, lorry can transport 2500 tons of carbon dioxide to northern moral from the firing equipment of southern moral.So as to store 2 Ten million KW's is distinguished and admirable, wherein the wind energy transformation is 1000 tons of methane, then the methane transports wind energy via gas transmission network Transport to Nan De.The method according to the invention auxiliary solves the dioxy in the case of " electric energy is converted to combustion gas (Power to Gas) " Change the acquisition problem of carbon.

For method for simplifying, especially economic aspect it is favourable can be, first not by all carbon dioxide separations.And Directly carbon dioxide can be dissolved under stress in aqueous condensate in a method flexible program, and with reaction Water is jointly stored and transported.Then, in the opening position of methane reduction, carbon dioxide and water is separated and are processed as storing up by water Carbon dioxide for electrolysis and is converted into methane by water with hydrogen as described.

In a flexible program of method, hot flue dust is compressed after being discharged from burner and then led to The carbon dioxide condensing dissolved when crossing the cooling of heat cycles loop by vapor and under stress.

Water/dioxide solution can be transported to the position for restoring methane.Here, by water and carbon dioxide separation and incite somebody to action Water hydrogenates carbon dioxide to form methane as the hydrogen that storage water is used to be electrolysed and electrochemically manufacture.

, also can be from the gas turbine or natural gas engine useless of district heating plant according to the method according to the invention Separation water and carbon dioxide in gas.In order to save consuming and energy, favourable can be, not by all carbon dioxide from flue dust Middle separation.

Herein by by the heat discharged in the water vapor condensation from methyl hydride combustion equally via heat exchanger export to The mode in heat cycles loop produces condensing heating system.

Therefore, present disclosure further relates to：By carbon dioxide from the flue dust of combustion of natural gas by means of mole phase Same carbon is converted into carbon monoxide (Bu Duaer balances) according to fluidized bed process, wherein the carbon is preferred from coal or coke； And by carbon monoxide with mol ratio 1:3 are converted into methane with the hydrogen from electrolysis；And that methane is directed back into natural gas is defeated In gas network.By the backflow of the methane so manufactured, second-time burning or release in terms of calculating by the carbon of coal.By Methane is carried out from the recovery in carbon dioxide in coal and wind energy or solar energy.The second-time burning of identical carbon causes carbon emission Decarburization, as this worldwide endeavours to reach in the resolution of the G7 summits in German Kloster Elmau in 2015 Target.

Carbon dioxide is changed with 4 moles of hydrogen when converting electrical energy into combustion gas and the efficiency that flows back accordingly is 30% to 35%, be converted to that the situation of combustion gas is different from above-mentioned electric energy, herein carbon monoxide used according to the invention and 3 moles Hydrogen react to form methane, wherein backflow efficiency be 50% to 60%.

In a flexible program of method, hot flue dust is also compressed when being discharged from burner, and subsequent Vapor is by means of the carbon dioxide condensing that dissolves under stress when being cooled down by heat cycles loop.

Water/dioxide solution can be transported to the opening position restored to methane.Here, by water and carbon dioxide separation simultaneously And hydrogenate carbon dioxide to form methane using water as the hydrogen that storage water is used to be electrolysed and electrochemically manufacture.

According to the present invention, 1 cubic metre of methane is obtained according to following formulas：

- 300g to 400g coal (according to Coal Quality)

The 1100g of-the flue dust from combustion of natural gas carbon dioxide

- 10KW to 12KW wind energy or solar energy, for electrochemically manufacture hydrogen (according to be added to electrolysis hydrogen, Amounts of hydrogen from coke-stove gas).

For chemical aspect in other words, burned carbon carbon burned in the form of carbon dioxide and not is anti-in returning Carbon monoxide middle should be formed, the carbon monoxide produces methane with hydrogen reaction.In terms of calculating, carbon is by second-time burning.

What is considered is about 5KW heat energy or 3KW electric energy, and the heat energy is produced by burning or discharging natural gas partial Or electric energy, the 1100g carbon dioxide in above-mentioned formula come from the natural gas partial.Hence it is advantageous to burn or release first Natural gas is put, and carbon dioxide is separated from burning gases, then the carbon dioxide is converted into coal and electrolysis hydrogen Methane.

The carbon dioxide being incorporated in methane causes the two of the motor vehicle of correlation when can be burnt in natural gas engine Aoxidize carbon emission.Natural gas engine is also used in district heating plant, so that can by means of the methane according to the present invention CO2 emission is reduced in heating system and in a mobile system indoors.

Will referring again to be：It can be stored and transported in natural gas transmission network according to the methane of the present invention, and The natural gas of equivalent can be extracted from gas transmission network.

The ecological benefits of the present invention are dual：Natural gas burns or discharged in a manner of without CO2 emission first. Then it is then described by restoring to obtain reproducible methane the carbon dioxide separated from the flue dust of combustion of natural gas before Methane discharges carbon dioxide when it burns, and the carbon dioxide is in advance by chemical combination in its generation.Thus, it is reproducible Methane is similar with biological methane in terms of its Ecology Action.

Reference paper：

The AI/2010 of 1.DE 102009018126 are open October 14

The AI/2013 of 2.WO 2013/152748 are open October 17

The AI/2013 of 3.DE 102012007136 are open October 10

Claims (according to the 19th article of modification of treaty)

1. one kind is used for the nytron that methane or long-chain are manufactured by coal or coke and (storage) electric energy and carbon dioxide The method of thing, wherein separating carbon dioxide in natural gas or the flue dust of methane or forming gas from burning or discharging, or turning Change methane and produce carbon dioxide in addition to hydrogen during natural gas and storing carbon dioxide and storage is added in Coal Gasification The carbon dioxide deposited is to manufacture forming gas, the admixture of gas being made up of carbon monoxide and hydrogen and by the titanium dioxide of addition Carbon (according to Boudouard reaction) reacts under conditions of Coal Gasification produces forming gas or carbon monoxide that hydrogen is consumed And carbon monoxide and the hydrogen by being obtained electrolysis water by electric energy are converted into the hydrocarbon of methane or long-chain, and The natural gas or methane or be changed into the coal of forming gas with without CO2 emission that the carbon dioxide wherein stored comes from Form is burned or release.

2. according to the method for claim 1, wherein the carbon dioxide stored is commonly used in Coal Gasification with vapor In, and 1 mole of carbon dioxide and vapor 1 mole of carbon is supplemented and the molar fraction of water and carbon dioxide from 1:0 reaches 0:1.

3. according to the method described in claim 1 and 2, it is characterised in that insert natural gas when manufacturing carbon monoxide.

4. the method according to claims 1 to 3, it is characterised in that compress flue dust and from cigarette by co 2 liquefaction Separated in dirt.

5. the method according to Claims 1-4, it is characterised in that accommodate and separate carbon dioxide in cold-trap.

6. according to the method described in claim 4 and 5, it is characterised in that the flue dust mixture compressed is passed through into low-temperature heat The circulation loop of system is cooled down and separated using carbon dioxide condensing and as liquid.

7. the method according to claim 4 to 6, it is characterised in that the flue dust and vapor are jointly compressed and Carbon dioxide is separated in a manner of being dissolved in water with the gas remained under stress.

8. the method according to claim 1 to 6, it is characterised in that by the carbon dioxide of the liquid in forbay or incite somebody to action The carbon dioxide of solid-state is stored and/or transported in heat-insulated container as so-called dry ice.

9. the method according to claim 1 to 8, it is characterised in that the aqueous condensate that will be separated from the flue dust Used as storage water in electrolysis.

10. the method according to claim 1 to 9, it is characterised in that in the condition of isolation air in first method step It is lower that by carbonization of coal and in second method step, caused coke and carbon dioxide conversion are carbon monoxide, and from general Cleaned by Hydrogen Separation in the coke-stove gas obtained during carbonization of coal and by means of carbon monoxide and with adding what is also needed to Hydrogen from electrolysis is converted into the hydrocarbon of methane or long-chain.

11. the method according to claim 1 to 10, it is characterised in that be stored in caused in addition to hydrogen in electrolysis water Oxygen, and the oxygen is used for combustion air in conbustion synthesis gas and times of natural gas, and after by water condensation Storing carbon dioxide.

12. according to the method for claim 1, it is characterised in that burnt in a manner of without CO2 emission/discharge methane Or natural gas, wherein the carbon dioxide formed be converted to carbon monoxide and by carbon monoxide use by wind energy and solar energy by Methane is converted into the hydrogen of electrolysis water manufacture and methane is directed back in natural gas transmission network.

13. according to the method described in claim 1 to 12, it is characterised in that carbon dioxide is added what is run with natural gas Separated in hot equipment, wherein will compress and will be added by compression from the flue dust (according to heat pump principle) of aqueous condensate release The gas of heat is cooled down by heat cycles loop while by the carbon dioxide condensing in flue dust and by carbon dioxide Separated as liquid with the gas remained.

14. the method according to claim 1 to 13, it is characterised in that in the hydrogen for the motor vehicle with fuel cell Carbon dioxide is obtained at gas deposit station, is at the hydrogen deposit station in converter and natural gas is decomposed into hydrogen and titanium dioxide Carbon.

15. a kind of equipment for manufacturing methane, the equipment includes：

(1) forbay or heat-insulated container to be to accommodate with transport liquid, gaseous or solid-state carbon dioxide,

(2) it is used for the device for manufacturing forming gas, wherein adding carbon dioxide of the section store in (1) in Coal Gasification simultaneously And the carbon dioxide is converted into carbon monoxide,

(3) electrolyzer, it converts electrical energy into hydrogen, and

(4) it is used for hydrocarbonization that the carbon monoxide obtained in (2) is converted into methane or long-chain with the hydrogen obtained from (3) Compound.

Claims

1. one kind is used for the method for manufacturing methane by coal or coke and (storage) electric energy and carbon dioxide, wherein titanium dioxide Flue dust of the carbon from natural gas or methyl hydride combustion and isolated from the flue dust, or when by methane or natural gas conversion The carbon dioxide and storing carbon dioxide are produced in addition to hydrogen, and wherein (to be stored) electric energy and be turned by electrolysis water It is changed into hydrogen, it is characterised in that the carbon dioxide of storage and the carbon of coal are changed into an oxygen at a temperature of higher than 800 DEG C Change carbon, wherein carbon dioxide and on the one hand carbon and on the other hand balancing between carbon monoxide, so-called Bu Duaerping Weighing apparatus is located at carbon monoxide side and carbon monoxide is converted into methane and first with the hydrogen from electrolysis water in subsequent reaction Alkane is imported into natural gas transmission network.

2. according to the method for claim 1, it is characterised in that add carbon dioxide simultaneously when manufacturing forming gas by coal And obtain the forming gas that hydrogen is consumed.

4. the method according to claims 1 to 3, it is characterised in that compress flue dust and divide to liquefaction from the flue dust From carbon dioxide.

5. method according to any one of claim 1 to 4, it is characterised in that accommodate and separate titanium dioxide in cold-trap Carbon.

6. method according to any one of claim 1 to 5, it is characterised in that pass through the flue dust mixture compressed The circulation loop of low-temperature heating system is cooled down and separated using carbon dioxide condensing and as liquid.

7. the method according to claim 1 to 5, it is characterised in that the flue dust and vapor are jointly compressed and Carbon dioxide is separated in a manner of being dissolved in water with the gas remained under stress.

8. the method according to claim 1 to 7, it is characterised in that by the carbon dioxide of liquid or in aqueous condensate The carbon dioxide storage of middle dissolving is stored up in forbay or using the carbon dioxide of solid-state as so-called dry ice in heat-insulated container Deposit and/or transport.

10. the method according to claim 1 to 9, it is characterised in that in the condition of isolation air in first method step It is lower that by carbonization of coal and in second method step, caused coke and carbon dioxide conversion are carbon monoxide, and from general Cleaned by Hydrogen Separation in the coke-stove gas obtained during carbonization of coal and by means of carbon monoxide and with adding what is also needed to Hydrogen from electrolysis is converted into methane.

12. the method according to claim 1 to 11, it is characterised in that burn/discharge in a manner of without CO2 emission Coal or natural gas.

15. according to the method described in claim 1 and 3 to 14, it is characterised in that obtain one cubic metre of first according to following formulas Alkane：

- 300g to 400g coal or coke (being weighed according to the carbon element content of coal)

The 1100g carbon dioxide of-flue dust from combustion of natural gas or when natural gas is decomposed into hydrogen and carbon dioxide Caused carbon dioxide in converter；

- the hydrogen that electrolysis manufacture is passed through by 10KW to 12KW wind energies or solar energy.

16. a kind of equipment being used for according to claim 1 to the 15 manufacture methane, the equipment include：

(1) it is used for the device for reaching Bu Duaer balances in carbon monoxide side, carbon dioxide is with coming from coal in said device The carbon of charcoal or coke is reacted；With

(2) it is used for the device for making carbon monoxide form methane by the hydrogen from electrolysis water.